Naphthyldimethylene spaced phenyl glycidyl ethers



United States Patent 3,290,269 NAPHTHYLDIMETHYLENE SPACED PHENYL GLYCIDYL ETHERS John OBrochta, Pittsburgh, Pa., assignor to Koppers Company, Inc., a corporation of Delaware No Drawing. Filed Apr. 1, 1963, Ser. No. 269,779

.- 2 Claims. (Cl. 260-47) This invention relates generally to novel resins and more particularly to novel epoxy resins.

Epoxy resins are finding wide use as ingredients in coating, adhesive, potting, and encapsulating compositions. A catalyst curing agent or hardener such for example as an anhydride, an amine, or a BF complex in the composition reacts with the epoxy resin to convert the resin to the ultimate product.

DAlelio Patent No. 2,658,884 describes an epoxy resin that is aromatic in character but has only carbont-o-carbon bonds between between the phenyl compounds. Thus, the phenyl or alkyl phenyl groups which contain the glycidyl ethers are connected by methylene bridges. The polymeric is represented by a series of repeating units. The general structure is illustrated as:

OH I it ii iii H ---oH X t t Y wherein R is a substituent of the class consisting of alkyl,

aryl, aralkyi, alkaryl, and alkary|l groups or chlorene or hydrogen. X and- Y are substituents selected from the class consisting of hydrogen, chlorene, and alkyl and hydroxyl groups.

The foregoing resins are prepared by condensing a phenol with an aldehyde under acid conditions to produce a novolak resin and then the novolak resin epoxidized by condensation with epichlorhydrin under alkaline conditions.

There has now been discovered in accordance with this invention novel resins in which the phenyl glycidyl others are separated by the large and inert groupnaphthyldimethylene.

pared in accordance with the process described in United States Patent No. 1,910,462. Briefly, this involves the CH J X reaction of naphthalene, formaldehyde, andhydrogen chloride.

The bis(chloron1ethy l) naphthalene is condensed with a phenol, advantageously phenol or cresol, in the presence of a Friedel-Crafts catalyst at elevated temperatures. The resulting condensation product is characterized by the repeating units.

I" OH where n==3-8.

The condensate product is condensedwith epich-lorohydrin in the presence of an alkali metal hydroxide in accordance with the general procedure described in United States Patent No. 2,995,583.

The epoxy resins, when hardened by suitable catalysts, hardeners, and curing agents provide products which find use where high impact strength, good alkali resistance, and excellent electrical properties are required.

The invention will be illustrated further by the following examples:

Example I T o a flask equipped with a reflux condenser and a thermometer is charged a mixture of 900 grams of an aqueous solution of formaldehyde (30% strength) and 600 grams of concentrated hydrochloric acid, and 270 grams of naphthalene is added thereto. The mixture is then heated to reflux and with a stirring at current of gaseous hydrochloric acid is introduced for about 12 hours. After cooling, the solid product is separated from the mother liquor, washed with water and dried under vacuum. The crude ibis (chloromethyDnaphthalene is purified by recrystallization in acetone to yield about an equal mixture of the 1,4- and 1-5-is-omers of bis(chloromethyl) naphthalene.

To a one liter resin flask, equipped with stirrer, thermometer, heated dropping funnel and reflux condenser was charged 141 g. (1.5 m.) of phenol and 0.1 g. of ZnCl The mixture was heated to C. under an atmosphere of nitrogen and maintained at this temperature product calls for an ox-ox value of 6.2%. The product had the general structure:

rlr 1'1 Ill H Ho E t I/ a D 11(1) Ht: Ht) HO $11: (3H2 (III-I7 (]']Hg 0 o o 0 I I CH 'CH CH2 CH2 CH CH2 chlorobenzene (soluble at 70 C.) was added over a The foregoing has presented novel resins. As will be period of two hours. An immediate and vigorous evoluapparent to those skilled in the art, the novel resins protion of HCl occurred upon the addition of the his (chlorovide a great .arntount of flexibility as to molecular Weight methyDnaphthalene. After addition had been completed, and glycidyl radicals per molecule. For example, the nitrogen was bubbled through the reaction mixture while phenols which are condensed with the -bis(chloromethyl) the temperature was maintained at 135 C. until HCl naphthalene may be substituted phenols. Further, the evolution ceased. This required about one hour. The molecular weight may be controlled by ratio of phenol to mix was then devolatilized at a temperature of 170 C. the bis(chloromethyl)naphthalene. Advantageously, the and under a vacuum of 10 mm. of mercury. There was ratio ranges from 2 /2 moles of phenol per mole of his obtained 261.2 g. (94% theory) of a tan resin which was (chloromethyl)naphthalene to 10 moles of phenol per soluble in dichlorobenzene, acetone, epichlorohydrin, and mole of bis(chlorornethyl)naphthalene. The ratios are dilute odium hydroxide but only a tiall ol bl i m. not particularly critical except that with insufficient phenol, matic solvents such as toluene and benzene. It had a Solubility of the ingredients y Cmate PmblemS and molecular weight of 835, softening point (R. and B.) With too much phenol, undesirable by-products are proof 117 C. and a total hydroxyll content of 8.2%. The duced. Further flexibility, as far as the product, is instructure is illustrated below; creased in that by controling the extent of etherification,

(|)H ?H ()H OH OHGH1A-GH3-GH2 Cl1r-OHr To a two liter resin pot, equipped with a stirrer, therfree hydroxyl radicals may the present in the epoxy resin. mometer, dropping funnel, condenser and heated b rette, The extent of etherification can be controlled by control- Was charged 207 g. (1.0 eq.) the foregoing novel resin, 40 ling the amount of epichlorohydrin present for etherificaand 622 ml. (8.0 moles) epich'lorohydrin. The mixture was heated to 117 C., to obtain a clear solution, and then cooled to 84 C. Then 29 grams of sodium hydroxide (1.02 moles) were added as a 70% solution by means of the heated burette. One-half of the caustic was added over a period of thirty minutes at a temperature of 92- 96 C., under conditions of total reflux. The remaining caustic was added over a period of thirty minutes at a temperature of 991l0 C., the water distilled oif as rapidly as possible. The reaction mixture was devolatilized at 150 C. at a vacuum of 25 mm. mercury. Toluene (1030 ml.) was added and 100 ml. of added toluene was distilled. After cooling to 40 C., the mix was filtered and devolatilized at a residue temperature of 150 C. at a vacuum of 25 m. of mercury to yield 255 g.

(97% theory) of resin. The product was a slightly cloudy tan resin containing 5.5% ox-ax, 0.4% chlorine and havg a Durrans S1. of 92 C. Theory for the postulated tion and the amount of alkali metal hydroxide for the etherification.

I claim:

1. The novel epoxy resin:

where n=38.

2. The novel epoxy resin:

n=27 R=hydrogen or a methyl group No references cited.

WILLIAM H. SHORT, Primary Examiner.

Y T. D. KERWIN, Assistant Examiner. 

1. THE NOVEL EPOXY RESIN: 